A convenient route for the synthesis of various charged tetracyclic isoquinolizinium hexafluorostilbates was developed using AgSbF6/AuCl(PPh3) for the intramolecular addition of amine to alkyne. The described process is tolerant of a variety of functional groups and broadens the diversity of substrates with the use of 8-substituted tetracyclic isoquinolizinium salts.